Polyorganosilsesquioxane and process for preparing the same

ABSTRACT

Provided are polyorganosilsesquioxane and process for preparing the same. The polyorganosilsesquioxane is obtained by various methods including polymerization of an organosilanetriol as starting materials. The polyorganosilsesquioxane has convenience in handling and controlling the rate of polymerization, and structure of highly regular form, and be imparted high functionality and various characteristics as compared to a conventional polyorganosilsesquioxane.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to polyorganosilsesquioxane and a process for preparing the same, and more particularly, to polyorganosilsesquioxane having organosilanetriol as starting materials, and a process for preparing the same.

2. Description of the Related Art

With the development of high-level advanced technology, research into high-performance, multi-functional high-technology materials is being conducted in various fields. In particular, in research into novel polymeric materials, much attention has been paid to novel high-functional organic polymers, e.g., organic polymers having improved heat resistance and glass transition temperature (T_(g)), and technology of forming organic or inorganic hybrid materials, such as an organic and inorganic hybrid complex.

There are known many existing organic or inorganic hybrid materials. In particular, due to importance of thermal stability between organic polymer and inorganic polymer, keen attention is focused on polyorganosilsesquioxane, which is a high-heat-resistance polymer.

Polyorganosilsesquioxane was first introduced in an article of J. Am. Chem. Soc., 82, 6194 (1960) by Brown et al., and commercialized in trade names of “Glass-resin” and “SST-resin” by Owens Illinois and Gelest. However, polyorganosilsesquioxane is not being put into practical use as industrial material because of difficulties of controlling the polymer structure and adjusting the molecular weight thereof.

A highly regular ladder form of polyorganosilsesquioxane accounts for its improved performance properties. Thus, along with development of novel starting materials that can easily form a ladder-form structure, research into condensation methods thereof has been made in various fields of industry in various ways.

Among known methods of preparing polyorganosilsesquioxane, a representative method is to dehydrate and condense a precursor hydrolyzed product (oligomer), synthesized by hydrolyzing trichlorosilane or trialkoxysilane in the presence of alkali/acidic catalyst, thereby easily obtaining a low-molecular weight polymer (having a number-average molecular weight (M_(n)) of 20,000 to 30,000 and a degree of dispersion (M_(w)/M_(n)) of 3 to 5.

A conventional method of preparing polyorganosilsesquioxane using trichlorosilane will first be described. Oligomer produced by co-hydrolytic condensation when hydrolyzing trichlorosilane, the oligomer having of M_(n) of 1,000 to 2,000 and a polydispersity index value (PDI) of 2 to 5, has a complicated, diverse structure, compared to silanetriol which is a single structure. In the case of forming high-molecular weight oligomer, a three-dimensional network structure is easily formed by constructural deformity due to the presence of inter-hydroxy group, and the inherent structure of oligomer, having the following disadvantages: 1) The structure of produced polymer is uncontrollable; 2) It is difficult to adjust the molecular weight of produced polymer and to obtain high-molecular weight polymer; 3) The produced polymer loses high regularity, lowering solubility against solvent; and 4) Remaining low-molecular weight components may adversely affect the heat resistance and mechanical property of polymer.

A conventional process for preparing polyorganosilsesquioxane using trialkoxysilane is also advantageous from the viewpoint of handling convenience, such as controllability of a hydrolysis rate, compared to trichlorosilane. However, various studies reported that this process had the following disadvantages caused by the oligomer molecular deformity due to the presence of inter-hydroxy group, and by the presence of alkoxy group: 1) A polymer of a branch structure, rather than a ladder structure, is formed; 2) selection of catalyst used, amount of the selected catalyst, selection of reactant solvent, careful adjustment of pH of selected reactant solvent, and so on, are not easy to achieve; and 3) a three-dimensional network structure causes micro-gelation. These disadvantages may adversely affect preparation of highly regular silicon ladder-form polymer.

As described above, a great attention has been paid to polyorganosilsesquioxane and constant research into the same has been made. According to known various synthesizing methods, e.g., a sol-gel method, a ring-opening polymerization method or an equilibrium polymerization method, and research into the structure of polyorganosilsesquioxane, condensation thereof is very complicated and versatile, so that the structure of polymer cannot be sufficiently controlled. Thus, even a product commercially available in the trade name of glass resin, also called T-type resin, cannot meet several requirements to be used as a novel industrial material, which becomes impediment to practical use.

Requirements of novel industrial materials using organic or inorganic hybrid materials are: a low dielectric constant of 2 to 3; excellent thermal stability such as a pyrolysis starting temperature of 400° C. or higher; low hygroscopicity; a low thermal expansion coefficient; excellent gap filling capability; excellent bondability.

To overcome the above-described problems, the present inventors proposed polyphenylsilsesquioxane having high regularity and crystallinity, which cannot be controlled by conventional methods, using high-purity organosilanetriol as a starting material, rather than oligomer having various molecular weights and structures.

However, there is still a need for polyorganosilsesquioxane having high regularity/crystallinity.

SUMMARY OF THE INVENTION

It is an objective of the present invention to provide a novel high-technology inorganic material having excellent properties through development of new precursors, and preparation method thereof, the precursors being: 1) easy in handling; 2) capable of adjusting the rate of polymerization; 3) capable of uniformly distributing hydroxy groups at both ends of polymer; 4) capable of introducing R—SiO_(3/2) to the main chain of polymer with high regularity; 5) easily capable of adjusting the crosslinking structure of polymer, specifically, crosslinkablity or crosslinking density; 6) capable of facilitating chemical modification by spreading the structure of polymer; 7) easily capable of forming nano-sized pores in the backbone of polymer; and 8) capable of imparting high functionality and versatile properties to polymer.

To accomplish the above objective of the present invention, there is provided polyorganosilsesquioxane and a process for preparing the same.

Polyorganosilsesquioxane according to the present invention is a compound represented by formula 1, 2 or 3:

wherein R₁ is a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 1 to 30 carbon atoms, an unsubstituted or substituted alicyclic hydrocarbon group having 1 to 30 carbon atoms, an unsubstituted or substituted silyl group having 1 to 30 carbon atoms, an unsubstituted or substituted allyl group having 1 to 30 carbon atoms, an unsubstituted or substituted acyl group having 1 to 30 carbon atoms, a vinyl group, an amine group, an acetate group or an alkali metal, and n is an integer of 2 to 300,000.

wherein R₁ is as defined above, R₃ is as defined as in R₁, l is a multiple integer of 2, ranging from 2 to 300,000, and m and n are integers from 2 to 300,000.

wherein R₁, R₃, l, m and n are as defined above.

Cyclictetraorganosilsesquioxane represented by formula 4 is provided as a precursor for preparing the compound represented by Formula 1, 2 or 3:

wherein R₁ is as defined above.

The process for preparing the cyclictetraorganosilsesquioxane represented by formula 4 provided as a precursor for preparing the polyorganosilsesquioxane according to the present invention can be expressed in the reaction scheme 1:

wherein R₁ is as defined above.

As expressed in the reaction scheme 1, the cyclictetraorganosilsesquioxane represented by formula 4 provided as a precursor for preparing the polyorganosilsesquioxane according to the present invention can be obtained by reacting organosilanetriol as a starting material in an organic solvent in the presence of a catalyst. In addition to the compound represented by Formula 1, compounds having various structures can be obtained by the above reaction, and high purity compounds can be obtained by separating and refining the obtained compounds by HPLC or recrystallization.

The organic solven used in the above reaction is not specifically limited as long as it can be generally used in the art, but acetone, toluene, n-hexane, THF or ether is preferably used.

As the catalyst used in the above reaction, NaOH, KOH, NaHCO3 or DCC (1,3-dicyclohexylcarbodiimide) is preferably used.

The reaction temperature is preferably 3 to 100° C., and the reaction time is preferably 1 to 200 hours.

The cyclictetraorganosilsesquioxane represented by formula 4 is reacted as represented by the reaction scheme 2, thereby obtaining the polyorganosilsesquioxane represented by Formula 1, 2 or 3:

wherein R₁, R₃, l, m and n are as defined above, and R₂, is a hydrogen atom, a methyl group, acetate, sodium or potassium, and X is a halogen atom.

The cyclictetraorganosilsesquioxane represented by formula 4 obtained as a precursor, is polymeric-condensed in an organic solvent, as represented by the reaction scheme 2 by the conventional method, thereby obtaining the polyorganosilsesquioxane represented by Formula 1, 2 or 3.

The polymeric-condensation method used in step (A), (B) or (C) of the reaction scheme 2 is not specifically limited, and various methods including heating, light radiation, electron beam scanning, microwave radiation and the like may be used. In the case of adding a catalyst, a compound having a large value of n can be obtained.

The compound represented by Formula 4 of the reaction scheme 2 is preferably in the range of 5 to 300 parts by weight, preferably 10 to 100 parts by weight based on 100 parts by weight of organic solvent. If the amount of the compound represented by Formula 4 is less than 5 parts by weight, the polymeric-condensation may be retarded or the reaction is not fully carried out, and if greater than 300 parts by weight, gelation may undesirably occur during reaction.

The catalyst used for facilitating the polymeric-condensation in step (A), (B) or (C) of the reaction scheme 2, is not specifically limited, but at least one material selected from the group consisting of alkali metal hydroxides such as sodium hydroxide, potassium hydroxide or cesium hydroxide, amines such as triethylamine, diethylene triamine, meth-butylamine, para-dimethylamine ethanol, triethanol amine, or quaternary ammonium salts, and fluorides. The catalyst used for polymeric-condensation is preferably in the range of 0.001 to 5 parts by weight, more preferably 0.001 to 1 part by weight based on 100 parts by weight of the compound represented by Formula 4.

The organic solvent used in the above reaction of the reaction scheme 2 is not specifically limited as log as it can be generally used in the art, but THF, benzene, chlorobenzene, xylene, methylisobutylketone (MIBK), dimethylformamide is (DMF), N-methylpyrrolidone (NMP), 1,4-dioxane, dimethylacetamicle (DMAC), acetone, or toluene is preferably used.

In step (A), (B) or (C) of the reaction scheme 2, the reaction temperature is preferably 50 to 350° C., more preferably 100 to 150° C. The reaction time is preferably 1 to 50 hours in the case of using a catalyst. In the case of not using any catalyst, the reaction temperature is preferably 150 to 350° C., and the reaction time is preferably 1 to 30 hours. If the reaction temperature is out of this range, the efficiency of the polymeric-condensation cannot meet industrial requirement.

Also, if the purity of the compound represented by Formula 2 for polymeric-condensation, is greater than or equal to 90%, a high molecular weight polymer, that is, M_(n)>500,000, can be obtained by the phase transition method.

In more detail, the process of each polymeric-condensation of the reaction scheme 2 will now be described.

In step (A) of the reaction scheme 2, the compound represented by Formula 4 is polymeric-condensed without additives, for dehydration and polymerization of hydroxy groups at both terminals, thereby obtaining the compound represented by Formula 1.

In step (B) of the reaction scheme 2, the compound represented by Formula 4, which is a precursor, (R₂O)₂Si(R₃)₂, which is a compound represented by Formula 6, and X₂Si(R₃)₂, which is a compound represented by Formula 7 are reacted. Here, a hydroxy group of the compound represented by Formula 4 and an alkoxy group of the compound represented by Formula 6 or X of the compound represented by Formula 7 are bonded to each other, thereby obtaining the compound represented by Formula 2. In particular, in the case of using the compound represented by Formula 6 as a reactant, alkali metal hydroxide is preferably used as the catalyst for polymeric-condensation

In step (C) of the reaction scheme 2, the compound represented by Formula 4, which is a precursor, (R₂O)₂Si(R₃, which is a compound represented by Formula 8, and X₃SiR₃, which is a compound represented by Formula 9 are reacted. Here, a hydroxy group of the compound represented by Formula 4 and an alkoxy group of the compound represented by Formula 8 or X of the compound represented by Formula 9 are bonded to each other, thereby obtaining the compound represented by Formula 3. In particular, in the case of using the compound represented by Formula 8 as a reactant, alkali metal hydroxide is preferably used as the catalyst for polymeric-condensation

The polyorganosilsesquioxane represented by Formulas 1 through 3 according to the present invention have a high solubility to a general organic solvent, and is soluble in organic solvents including aromatic hydrocarbons such as toluene, xylene, benzene or chlorobenzene, hydrocarbons such as methylene chloride or chloroethane, ethers such as THF, 1,4-dioxane, diethylether or dibutylether, ketones such as acetone, methyethylketone or methyletherketone, esters, or dimethylformamide.

In the present invention, R₁ and R₂ are independently a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 1 to 30 carbon atoms, an unsubstituted or substituted alicyclic hydrocarbon group having 1 to 30 carbon atoms, an unsubstituted or substituted silyl group having 1 to 30 carbon atoms, an unsubstituted or substituted allyl group having 1 to 30 carbon atoms, an unsubstituted or substituted acyl group having 1 to 30 carbon atoms, a vinyl group, an amine group, an acetate group or an alkali metal, preferably a lower alkyl such as a hydrogen atom, a methyl group, an ethyl group or a propyl group, a phenyl group, a phenol group, a chlorophenyl group, vinyl group, carboxyl group, a trimethylsilyl group, acetate or alkali metal, and more preferably a hydrogen atom, a methyl group, a vinyl group or a trimethylsilyl.

As described above, according to the present invention, unlike in conventional polyorganosilsesquioxane obtained by heat-condensing olygomer prepared by hydrolyzing conventional trichlorosilane or triethoxysilane, an organosilanetriol is first reacted to obtain cyclictetraorganosilsesquioxane, which is a precursor, and then polymeric-condensed to obtain polyorganosilsesquioxane, thereby synthesizing a highly-regular ladder-form polymer having repeating units of cyclotetraorganosilsesquioxane.

As described above, since Si—O—Si bonds and ladder-form structures are easily formed in the main chain of polymer with high regularity, high-heat-resistance can be maintained. Also, since inter-hydroxy group structures or defects existing in the main chain of polymer can be reduced no thermal treatment is required and various functional side chains (e.g., a photosensitive group or dealkyl reactive group) can be introduced. In particular, the physical property of polymer depending on a composition ratio of the introduced side chains, e.g., a difference in the ratio of phenyl to methyl, can be changed, and new polymeric molecules can be designed. Since terminal-silanol groups can be arranged regularly at the terminal of polymer so that the amount of organic polymer introduced can be adjusted in preparing organic or inorganic hybrid materials, thereby easily preparing an organic or inorganic copolymer.

In particular, the polyorganosilsesquioxane prepared according to the present invention has a unique molecular structure, that is, the ratio of siloxane (Si—O—Si) bonds and rigid ladder-form structures (R—SiO_(3/2)) present in the main chain of the polyorganosilsesquioxane prepared according to the present invention is 90% more than in the conventional polyorganosilsesquioxane, the percentage being represented by {no.of R—SiO_(3/2))+(no.of hydroxy groups+no.of terminal−silanol groups)×100}.

Thus, the polyorganosilsesquioxane prepared according to the present invention exhibits high solubility to a general organic solvent, and has excellent anti-wearability, low surface tension, optical transparency, low dielectric constant of 3.0 or less, low absorption ratio, excellent gap filling capability and so on. Also, the polyorganosilsesquioxane prepared according to the present invention is excellent in view of adhesion to glass or metal, e.g., aluminum, copper or titanium, electric insulation, water drainage, chemical resistance or transparency, by introducing different side chains, and can be commercially applicable in a wide range of industrial materials.

The polyorganosilsesquioxane prepared according to the present invention can be used in various fields: UV curable resins and silane compounds are widely used; and glass resins are also used in some fields. Materials of the polyorganosilsesquioxane prepared according to the present invention include polycarbonate, acryl resin, diethylglycolbisalkylcarbonate (in the trade name of “CR-39”) and so on. The polyorganosilsesquioxane prepared according to the present invention can be used for plastic, sunglasses, protective glasses, gauges, automobile lamps, aircraft windows or bulletproof glass. Also, the polyorganosilsesquioxane prepared according to the present invention can be used for thermally treating glass lenses with glass resin.

Further, the polyorganosilsesquioxane prepared according to the present invention is excellent in view of electric insulation, heat resistance, low absorption, planarization of a spin-on glass (SOG) solution, thereby being adapted to electronic usage. For example, the polyorganosilsesquioxane prepared according to the present invention is a general-purpose material that can be used as a protective coating for a thin film, an interlayer dielectric film in LSI multiple wiring, a low dielectric material, a multiple insulation film, an LCD insulator film and the like.

Recently, as a highly integrated semiconductor device has become narrower in line space, the thickness of formed coating layers unavoidably increase, resulting in cracks. Generation of cracks is presumably caused by the following factors: 1) thermal curing contraction stress generated when inter-hydroxy groups or terminal-silanol groups are mutually condensed; and 2) a difference in thermal stress depending on a difference in the thermal expansion coefficient among a cured film, an aluminum wiring and a silicon wafer. In the present invention, since the presence ratio of inter-hydroxy groups is low, a reaction occurring at the terminal can be prevented by introducing silylation or double bond into the terminal-silanol group, and new functionality of an organic-inorganic hybrid material can be attained by introducing other organic polymer, specifically polyimide, polyamide, PMMA, polyacryl, polycarbonate, polystyrene or polyurethane.

Further, the polyorganosilsesquioxane prepared according to the present invention is soluble in various solvents to form a thin film easily and has a high level of hardness. Also, since the polyorganosilsesquioxane prepared according to the present invention can form a highly transparent thin film, it can be commercialized together with optically functional organic polymers, thereby increasing the long-term reliability of optical fiber. Also, since the polyorganosilsesquioxane prepared according to the present invention is used as a material for forming a coating on the surface of a resistor, it can be applied for electric/electronic materials.

Also, the polyorganosilsesquioxane prepared according to the present invention can be used as a metal release agent in plastic molding plastic, e.g., urethane reactive injection molding (RIM), or in manufacturing glass. Further, a mixture of RTV and the polyorganosilsesquioxane prepared according to the present invention can be used as a tile adhesive agent or outer surface coating of a space shuttle, a binder of optical fiber, and the like, and can be used for heat-resistive coating materials owing to its heat resistance and corrosion resistance.

The applicability of the final product according to the present invention will be boundlessly extended, not limited to the above-described fields, along with the development of advanced technology.

DETAILED DESCRIPTION OF THE INVENTION

For better understanding of the present invention, the invention will now be described in detail through preferred embodiments with reference to the accompanying drawings. The present invention may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, those embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

EXAMPLE 1 Preparation of a Compound Represented by Formula 4; (cyclictetraphenylsilsesquioxane) (R₁=phenyl)

A magnetic stirrer was installed in a 250 ml round bottom flask and dried with flame while passing dried nitrogen gas. 25 g of phenylsilanetriol (PST) having a result of ¹H NMR analysis shown in FIG. 1, and 1.25 g of sodium hydrocarbonate as a catalyst, were dissolved in 80 ml of chloroform, and insoluble materials were filtered for removal, and the filtrate was concentrated to a half. The concentrated chloroform solution was recrystallized at −10° C. for 3 months, thereby obtaining colorless, clear, needle-shaped crystalline cyclictetraphenylsilsesquioxane (yield: 88%).

The obtained needle-shaped crystal was vacuum-dried at −10° C. for 4 hours to be used as an analysis sample.

¹H NMR (500 MHz/CDCl₃): δ 7.11˜7.8(m, Si-Ph), 2.2˜2.8(s, Si—OH) ppm

IR(KBr): 3600˜3200(Si—OH), 3080˜2940(CH), 1435(Si-Ph), 1050(O—Si-Ph), 1150(O—Si), 750, 700(Ph) cm⁻.

²⁹Si NMR (99.3 MHz/CDCl₃): δ −64.1 ppm (Ph-T₂(OH)₁).

GPC (PST): M_(n)=640, M_(w)/M_(n)=1.0.

XRD: 2θ=5.71, 7.77 (Si—O), 19.52, 18.12 (Si-Ph).

EXAMPLE 2 Siloxyl Capping Reaction of Cyclotetraphenylsilsesquioxane

Another method of ascertaining the structure of cyclotetraphenylsilsesquioxane obtained in Example 1 will now be described.

A 20 ml dropping funnel was connected to a 50 ml round bottom flask and dried with flame while passing dried nitrogen gas. Subsequently, 0.33 g of cyclotetraphenylsilsesquioxane obtained in Example 1 was dissolved in 10 ml of distilled cycloxene, 0.17 g of a catalyst N(CH₂CH₃)₃ was then added thereto and then agitated at room temperature for 1 hour. 0.13 9 of (CH₃)₃SiCl was dissolved in 10 ml of cycloxene and then dropped using a dropping funnel to carry out a siloxy capping reaction. After completion of the reaction, trimethyl salts were filtered for removal, and then cycloxene was vacuum-dried, thereby obtaining a white product.

¹H NMR (500 MHz/CDCl₃): δ 7.11˜7.8(m, Si—C₆H₅), 0.2(s, (CH₃)₃—Si) ppm.

(Ph/Me₃ ratio: 35.8/19.2≈5/9).

²⁹Si NMR (99.3 MHz/CDCl₃): δ −37(s, Si—(CH₃)₃), −83 (s, Ph-T₃) ppm.

EXAMPLE 3 Preparation of a Compound Represented by Formula 1; (polyphenylsilsesquioxane) (R₁=phenyl)

A Dean Stark tube was installed in a 50 ml round bottom flask and dried with flame under a nitrogen atmosphere. 5 g of the cyclictetraphenylsilsesquioxane obtained in Example 1 and 5.0 mg of KOH were put into the flask, and 38 ml of toluene was added thereto to dissolve the cyclictetraphenylsilsesquioxane. Subsequently, the resultant was reacted at a reflux temperature of toluene for 38 hours. After completion of the reaction, the reactant was dropped to an excess of methanol and agitated for 30 minutes to filter the precipitate, thereby obtaining white powder of a desired product (yield: 98%).

The product was vacuum-dried at 50° C. for 10 hours to be used as an analysis sample.

¹H NMR (500 MHz/CDCl₃): δ 7.11˜7.8 (s, Si-Ph) ppm.

IR (KBr): 3080˜2940 (CH), 1435 (Si-Ph), 1050(O—Si-Ph), 1150(O—Si), 750, 700 (Ph) cm⁻.

²⁹Si NMR (99.3 MHz/CDCl₃): δ 83.7 ppm.

XRD: 2θ=5.71, 7.96 (si—O), 24.87, 22.69, 19.52, 18.12 (Si-Ph)

EXAMPLE 4 Preparation of a Compound Represented by Formula 4 (cyclicietra(trimethylsilyl)silsesquioxane) (R₁=trimethylsilyl)

The process was carried out in the same manner as in Example 1, except that 1,1,1-trimethyl-2,2,2-triol disilane that can be confirmed as a starting material, was used instead of phenylsilanetriol.

¹H NMR (500 MHz/CDCl₃): δ 0.1 (s, Si—Si-Me₃), 4.4 (s, Si—OH) ppm

²⁹Si NMR (99.3 MHz/CDCl₃): δ −(s, Si-Me) ppm

GPC (PST): M_(n)=490, M_(w)/M_(n)=1.01

EXAMPLE 5 Photoreaction Process of a Compound Represented by Formula 1 (poly(trimethylsilyl)silsesquioxane) (R₁=trimethylsilyl)

5 g of cyclictetra(trimethylsilyl)silsesquioxane obtained in Example 4 was dissolved in 20 ml of cyclohexane and exposed to a low temperature mercury lamp for 3 minutes while being violently agitated. After completion of the reaction, the reactant was dropped to an excess of methanol and agitated for 30 minutes to filter the precipitate, thereby obtaining white powder of a desired product (yield: 97%).

The product was dried with a nitrogen gas at 3° C. to be used as an analysis sample. As the analysis result, it was confirmed that the obtained product was the compound represented by Formula 1 (poly(trimethylsilyl)silsesquioxane).

¹H NMR (500 MHz/CDCl₃): δ −0.1˜0.4 (s, Si—Si-Me₃)

²⁹Si NMR (99.3 MHz/CDCl₃): δ −62.4˜68.0 (s, Si-Me) ppm

EXAMPLE 6 Polymeric-condensation of Compound Represented by Formula 1 (poly(trimethylsilyl)silsesquioxane) (R₁=trimethylsilyl)

The polymeric-condensation process was carried out in the same manner as in Example 3, except that cyclictrimethylsilyl obtained in Example 1, was used instead of cyclictetraphenylsilsesquioxane of Example 3, thereby obtaining white powder of a desired product (yield: 98%).

GPC (PST): M_(n)=36,000, M_(w)/M_(n)=1.4

¹H NMR (500 MHz/CDCl₃): δ −0.8˜0.4 (s, Si—Si-Me₃) ppm

EXAMPLE 7 Preparation of Compound Represented by Formula 2 (R₁=phenyl, R₃=methyl)

A reflux condenser, 20 ml 300 ml dropping funnel, and Dean Stark tube were placed in a 1000 ml four-necked round bottom flask and dried with flame under a nitrogen atmosphere. 50 g of cyclotetraphenylsilsesquioxane obtained in Example 1 was put into the flask, dissolved in 380 ml of toluene and reacted at room temperature while slowly dropping 46 g of dichloromethylsilane using a dropping funnel. After completion of the 4-hour reaction, the reaction temperature was reduced to 3° C., 250 ml of secondary distilled water was dropped into the reactant solution for 1-hour hydrolysis, and then 5 mg of KOH as a polymerization catalyst was added. Then, the reactant was reacted at a reflux temperature for 38 hours. After completion of the reaction, the reactant was dropped into an excess of methanol, agitated for 30 minutes, and then filtered the produced precipitate, thereby obtaining white powder of a desired product (yield: 96%).

GPC(PST): M_(n)=42,000, M_(w)/M_(n)=1.37

¹H NMR (500 MHz/CDCl₃): δ −0.8˜0.4 (s, Si-Me), −7.1˜7.86 (s, Si-Ph) ppm

²⁹Si NMR (99.3 MHz/CDCl₃): δ −54.8 (Me-T₂), −80.7 (s, Ph-T₃) ppm

EXAMPLE 8 Preparation of Compound Represented by Formula 3 (R₁=phenyl, R₃=methyl)

A reflux condenser, 20 ml/300 ml dropping and Dean Stark tube were placed in a 1000 ml four-necked round bottom flask and dried with flame under a nitrogen atmosphere. 50 g of cyclotetraphenylsilsesquioxane obtained in Example 1 was put into the flask, dissolved in 380 ml of toluene and reacted at room temperature while slowly dropping 54 g of trichloromethylsilane using a dropping funnel. After completion of the 1-hour reaction, the reaction temperature was reduced to 3° C., 250 ml of secondary distilled water was dropped into the reactant solution for 1-hour hydrolysis, and then 5 mg of KOH as a polymerization catalyst was added. Then, the reactant was reacted at a reflux temperature for 38 hours. After completion of the reaction, the reactant was dropped into an excess of methanol, agitated for 30 minutes, and then filtered the produced precipitate, thereby obtaining white powder of a desired product (yield: 98%).

The product was thermally hardened at 150° C. under 4 Torr for 1 hour to be used as an analysis sample.

GPC(PST): M_(n)=42,000, M_(w)/M_(n)=1.37

¹H NMR (500 MHz/CDCl₃): δ −0.8˜0.4 (s, Si-Me), −7.1˜7.86 (s, Si-Ph) ppm

IR (KBr): 3080˜2940 (CH), 1600, 1435, 1120 (Si-Ph), 1050, 1150 (O—Si), 750, 700 (Ph), 1275, 800(Si-Me) cm¹

²⁹Si NMR (99.3 MHz/CDCl₃): δ −56 (s, Me-T₂), 64.6 (s, Me-T₃), 80.7 (s, Ph-T₃) ppm

EXAMPLE 9 Preparation of Compound Represented by Formula 2 (R₁=phenyl, R₃=methyl)

A reflux condenser, 100 ml dropping funnel and Dean Stark tube were placed in a 500 ml four-necked round bottom flask and dried with flame under a nitrogen atmosphere. 50 g of cyclotetraphenylsilsesquioxane obtained in Example 1 was put into the flask and dissolved in 380 ml of toluene, 0.5 ml of HCl as a reaction catalyst was added thereto and reacted at room temperature for 38 hours while slowly dropping 54 g of dimethoxymethylsilane using a dropping funnel. Thereafter, the reactant solution was further reacted at a reflux temperature of toluene for 72 hours. After the completion of the reaction, the reactant was dropped into an excess of methanol, agitated for 30 minutes, and then filtered the produced precipitate, thereby obtaining white powder of a desired product (yield: 87%).

GPC(PST): M_(n)=28,000, M_(w)/M_(n)=1.62.

¹H NMR (500 MHz/CDCl₃): δ −0.8˜0.4 (s, Si-Me), −7.1˜7.8 (s, Si-Ph) ppm

²⁹Si NMR (99.3 MHz/CDCl₃): δ 54.0 (s, Me-T₂), −79.4 (s, Ph-T₃) ppm

EXAMPLE 10 Preparation of Compound Represented by Formula 3 (R₁=phenyl, R₃=methyl)

A reflux condenser, 100 ml dropping funnel and Dean Stark tube were placed in a 1000 ml four-necked round bottom flask and dried with flame under a nitrogen atmosphere. 50 g of cyclotetraphenylsilsesquioxane obtained in Example 1 was put into the flask and dissolved in 380 ml of toluene, 0.7 ml of HCl as a reaction catalyst was added thereto and reacted at room temperature for 38 hours while slowly dropping 54 g of trimethoxymethylsilane using a dropping funnel. Thereafter, the reactant solution was further reacted at a reflux temperature of toluene for 72 hours. After the completion of the reaction, the reactant was dropped into an excess of methanol, agitated for 30 minutes, and then filtered the produced precipitate, thereby obtaining white powder of a desired product (yield: 84%).

The product was thermally hardened at 150° C. under 4 Torr for 1 hour to be used as an analysis sample.

GPC(PST): M_(n)=22,000, M_(w)/M_(n)=1.78

¹H NMR (500 MHz/CDCl₃): δ −0.8˜0.4 (s, Si-Me), −7.1˜7.86 (s, Si-Ph) ppm

²⁹Si NMR (99.3 MHz/CDCl₃): δ 54 (s, Me-T₂), −62.6 (s, Me-T₃), −79.7 (s, Ph-T₃) ppm

While the present invention has been described in conjunction with the preferred embodiments, these embodiments are presented for illustrative purposes only, and are not as a restriction on the scope of the invention as recited in the appended claims. 

What is claimed is:
 1. A compound represented by Formula 1:

wherein R₁ is a hydrogen atom, an unsubstituted or substituted silyl group having 1 to 30 carbon atoms an amine group or an alkali metal, and n is an integer of 2 to 300,000.
 2. The compound according to claim 1, wherein R₁ is a hydrogen atom, or a trimethylsilyl group, and n is an integer from 1,000 to 100,000.
 3. A compound represented by Formula 2:

wherein R₁ and R₃ are independently a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 1 to 30 carbon atoms, an unsubstituted or substituted alicyclic hydrocarbon group having 1 to 30 carbon atoms, an unsubstituted or substituted silyl group having 1 to 30 carbon atoms, an unsubstituted or substituted allyl group having 1 to 30 carbon atoms, an unsubstituted or substituted acyl group having 1 to 30 carbon atoms, a vinyl group, an amine group, an acetate group or an alkali metal, I is a multiple integer of 2, ranging from 2 to 300,000, and m and n are integers from 2 to 300,000.
 4. The compound according to claim 3, wherein R₁ and R₃ are independently a hydrogen atom, a methyl group, a phenyl group or a trimethylsilyl group.
 5. A compound represented by Formula 3:

wherein R₁ and R₃ are independently a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 1 to 30 carbon atoms, an unsubstituted or substituted alicyclic hydrocarbon group having 1 to 30 carbon atoms, an unsubstituted or substituted silyl group having 1 to 30 carbon atoms, an unsubstituted or substituted allyl group having 1 to 30 carbon atoms, an unsubstituted or substituted acyl group having 1 to 30 carbon atoms, a vinyl group, an amine group, an acetate group or an alkali metal, l is a multiple integer of 2, ranging from 2 to 300,000, and m and n are integers from 2 to 300,000.
 6. The compound according to claim 5, wherein R₁ and R₃ are independently a hydrogen atom, a methyl group, a phenyl group or a trimethylsilyl group.
 7. A compound represented by Formula 4:

wherein R₁ is a hydrogen atom an unsubstituted or substituted silyl group having 1 to 30 carbon atoms, an unsubstituted or substituted allyl group having 1 to 30 carbon atoms, an unsubstituted or substituted acyl group having 1 to 30 carbon atoms, a vinyl group, an amine group, an acetate group or an alkali metal.
 8. The compound according to claim 7, wherein R₁ is a hydrogen atom, a vinyl group or a trimethylsilyl group.
 9. A process for preparing a compound represented by Formula 4 obtained by reacting a compound represented by Formula 5 in an organic solvent:

wherein R₁ is a hydrogen atom, an unsubstituted or substituted alicyclic hydrocarbon group having 1 to 30 carbon atoms, an unsubstituted or substituted silyl group having 1 to 30 carbon atoms, an unsubstituted or substituted allyl group having 1 to 30 carbon atoms, an unsubstituted or substituted acyl group having 1 to 30 carbon atoms, a vinyl group, an amine group, an acetate group or an alkali metal.
 10. The process according to claim 9, wherein the reacting is performed using a catalyst.
 11. The process according to claim 9, wherein the catalyst is one selected from NaOH, KOH, NaHCO₃ and 1,3-dicyclohexylcarbodiimide (“DCC”).
 12. A process for preparing a compound represented by Formula 1 by polymeric-condensing a compound represented by Formula 4 in an organic solvent:

wherein R₁ is a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, an unsubstituted or substituted alicyclic hydrocarbon group having 1 to 30 carbon atoms, an unsubstituted or substituted silyl group having 1 to 30 carbon atoms, an unsubstituted or substituted allyl group having 1 to 30 carbon atoms, an unsubstituted or substituted acyl group having 1 to 30 carbon atoms, a vinyl group, an amine group, an acetate group or an alkali metal, and n is an integer of 2 to 300,000.
 13. A process for preparing a compound represented by Formula 2 by polymeric-condensing a compound represented by Formula 4 and a compound represented by Formula 6 or a compound represented by Formula 7 in an organic solvent:

wherein R₁ and R₃ are independently a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 1 to 30 carbon atoms, an unsubstituted or substituted alicyclic hydrocarbon group having 1 to 30 carbon atoms, an unsubstituted or substituted silyl group having 1 to 30 carbon atoms, an unsubstituted or substituted allyl group having 1 to 30 carbon atoms, an unsubstituted or substituted acyl group having 1 to 30 carbon atoms, a vinyl group, an amine group, an acetate group or an alkali metal, l is a multiple integer of 2, ranging from 2 to 300,000, and m and n are integers from 2 to 300,000.
 14. A process for preparing a compound represented by Formula 3 by polymeric-condensing a compound represented by Formula 4 and a compound represented by Formula 8 or a compound represented by Formula 9 in an organic solvent:

wherein R₁ and R₃ are independently a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 1 to 30 carbon atoms, an unsubstituted or substituted alicyclic hydrocarbon group having 1 to 30 carbon atoms, an unsubstituted or substituted silyl group having 1 to 30 carbon atoms, an unsubstituted or substituted allyl group having 1 to 30 carbon atoms, an unsubstituted or substituted acyl group having 1 to 30 carbon atoms, a vinyl group, an amine group, an acetate group or an alkali metal, l is a multiple integer of 2, ranging from 2 to 300,000, and m and n are integers from 2 to 300,000.
 15. The process according to claim 12, wherein the polymeric-condensing reaction is one selected from the group consisting of heating, light radiation, microwave radiation and electron beam radiation.
 16. The process according to claims 13, wherein the polymeric-condensing reaction is one selected from the group consisting of heating, light radiation, microwave radiation and electron beam radiation.
 17. The process according to claim 14, wherein the polymeric-condensing reaction is one selected from the group consisting of heating, light radiation, microwave radiation and electron beam radiation.
 18. The process according to claim 12, wherein the amount of the compound represented by Formula 4 is 5 to 300 parts by weight based on 100 parts by weight of the organic solvent.
 19. The process according to claim 13, wherein the amount of the compound represented by Formula 4 is 5 to 300 parts by weight based on 100 parts by weight of the organic solvent.
 20. The process according to claim 14, wherein the amount of the compound represented by Formula 4 is 5 to 300 parts by weight based on 100 parts by weight of the organic solvent.
 21. The process according to claim 12, wherein the process is further performed in the presence of a polymeric-condensation catalyst.
 22. The process according to claim 13, wherein the process is further performed in the presence of a polymeric-condensation catalyst.
 23. The process according to claim 14, wherein the process is further performed in the presence of a polymeric-condensation catalyst.
 24. The process according to claim 21, wherein the polymeric-condensation catalyst is one selected from the group consisting of sodium hydroxide, potassium hydroxide, cesium hydroxide, triethylamine, diethylene triamine, meth-butylamine, para-dimethylamine ethanol, triethanol amine, quaternary ammonium salts, and fluorides.
 25. The process according to claim 22, wherein the polymeric-condensation catalyst is one selected from the group consisting of sodium hydroxide, potassium hydroxide, cesium hydroxide, triethylamine, diethylene triamine, meth-butylamine, para-dimethylamine ethanol, triethanol amine, quaternary ammonium salts, and fluorides.
 26. The process according to claim 23, wherein the polymeric-condensation catalyst is one selected from the group consisting of sodium hydroxide, potassium hydroxide, cesium hydroxide, triethylamine, diethylene triamine, meth-butylamine, para-dimethylamine ethanol, triethanol amine, quaternary ammonium salts, and fluorides.
 27. The process according to claim 24, wherein the catalyst used for polymeric-condensation is preferably in the range of 0.001 to 5 parts by weight, based on 100 parts by weight of the compound represented by Formula
 4. 28. The process according to claim 25, wherein the catalyst used for polymeric-condensation is preferably in the range of 0.001 to 5 parts by weight, based on 100 parts by weight of the compound represented by Formula
 4. 29. The process according to claim 26, wherein the catalyst used for polymeric-condensation is preferably in the range of 0.001 to 5 parts by weight, based on 100 parts by weight of the compound represented by Formula
 4. 